Anisotropic copoly(imide oxetane) coatings and articles of manufacture, copoly(imide oxetane)s containing pendant fluorocarbon moieties, oligomers and processes therefor

Patent metadata

Field	Value
Publication number	US-11760738-B2
Application number	US-202117487803-A
Country	US
Kind code	B2
Filing date	Sep 28, 2021
Priority date	Mar 30, 2011
Publication date	Sep 19, 2023
Grant date	Sep 19, 2023

Abstract

Copoly(imide oxetane) materials are disclosed that can exhibit a low surface energy while possessing the mechanical, thermal, chemical and optical properties associated with polyimides. The copoly(imide oxetane)s are prepared using a minor amount of fluorinated oxetane-derived oligomer with sufficient fluorine-containing segments of the copoly(imide oxetane)s migrate to the exterior surface of the polymeric material to yield low surface energies. Thus the coatings and articles of manufacture made with the copoly(imide oxetane)s of this invention are characterized as having an anisotropic fluorine composition. The low surface energies can be achieved with very low content of fluorinated oxetane-derived oligomer. The copolymers of this invention can enhance the viability of polyimides for many applications and may be acceptable where homopolyimide materials have been unacceptable.

First claim

What is claimed:

1. A copoly(amic acid oxetane) having the structure represented by:
—(G—A)—(D—A)—

wherein:
G is represented by the formula
—NH—R 1 —C(O)—O—J—C(O)—R 1 —HN—

wherein:
J is [CH 2 —CR 2 R 3 —CH 2 —O] m or
[(CH 2 —CR 2 R 3 —CH 2 —O) p —(R 6 —O) q —(CH 2 —CR 2 R 3 —CH 2 —O) r ] wherein R 6 is a substituted or unsubstituted aliphatic or aromatic moiety of 2 to 16 carbons;
R 1 is an aliphatic or aromatic hydrocarbon moiety of 1 to 10 carbon atoms;
R 2 is —H, —F, or an alkyl of 1 to 6 carbon atoms;
R 3 is —F, —R 4 H (n-a) F a , —R 5 —O—R 4 H (n-a) F a , or —O—R 4 H (n-a) F a , wherein R 4 is an alkyl or ether moiety of 1 to 30 carbons, R 5 is an alkyl moiety of 1 to 30 carbons, a is an integer of 3 to n, and n is twice the number of carbon atoms in the alkyl moiety plus 1;
m is between about 4 and 500, p is between about 4 and 150, q is between about 1 and 150; and
r is an integar;

A is represented by the formula
wherein:

L is a hydrocarbyl-containing moiety of 2 to 100 carbon atoms, optionally containing divalent radicals selected from the group consisting of oxygen, silyl, sulfur, carbonyl, sulfonyl, phosphonyl, perfluoro, tertiary amino, and imido;

D is represented by the formula
—NH—Z—NH—

wherein:
Z is a hydrocarbyl-containing moiety of 1 to 100 carbon atoms optionally containing divalent radicals selected from the group consisting of oxygen, sulfur, silyl, carbonyl, sulfonyl, phosphonyl, perfluoro, tertiary amino, and imido.

2. A polymer composite comprising a copolymer containing the copoly(amic acid oxetane) of claim 1 and a particulate filler, wherein the polymer composite has a water contact angle of at least 100° .

3. A process for making a copoly(amic acid oxetane) of claim 1 comprising:
a. reacting an oxetane oligomer of the formula
H—O—J—H

wherein
J is [CH 2 —CR 2 R 3 —CH 2 —O] m or
[(CH 2 —CR 2 R 3 —CH 2 —O) p— (R 6 —O) q— (CH 2 —CR 2 R 3 —CH 2 —O) r ], wherein R 6 is a substituted or unsubstituted aliphatic or aromatic moiety of 2 to 16 carbons;
R 2 is —H, —F, or an alkyl of 1 to 6 carbon atoms;
R 3 is —F, —R 4 H (n-a) F a , —R 5 —O—R 4 H (n-a) F a , or —O—R 4 H (n-a) F a , wherein R 4 is an alkyl or ether moiety of 1 to 30 carbons, R 5 is an alkyl moiety of 1 to 30 carbons, a is an integer of 3 to n, and n is twice the number of carbon atoms in the alkyl moiety plus 1;
m is between about 4 and 500, p is between about 4 and 150, q is between about 1 and 150; and
r is an integer;
with an acyl reagent of the formula O 2 N—R 1 C(O)X,
wherein R 1 is an aliphatic or aromatic hydrocarbon moiety of 1 to 10 carbon atoms and X is selected from the the group consisting of bromide, chloride and iodide, —H, —OH, and —OR 8 , wherein R 8 is an alkyl of 1 to 3 carbon atoms to provide a nitro-terminated oligomer;

b. hydrogenating the nitro-terminated oligomer under hydrogenation conditions including the presence of a hydrogenation catalyst to convert nitro moieties to amine moieties and provide a diamine-terminated oligomer; and
c. reacting the diamine-terminated oligomer with at least one of
(i) a dianhydride of the formula
O(C(O)) 2 —L—(C(O)) 2 O   (I)

wherein
L is a hydrocarbyl-containing moiety of 2 to 100 carbon atoms, optionally containing divalent radicals selected from the group consisting of oxygen, silyl, sulfur, carbonyl, sulfonyl, phosphonyl, perfluoro, tertiary amino, and imido;

in the presence of one or more diamines of the formula
—NH—Z—NH—  (II)

wherein:
Z is a hydrocarbyl-containing moiety of 1 to 100 carbon atoms, optionally containing divalent radicals selected from the group consisting of oxygen, sulfur, silyl, carbonyl, sulfonyl, phosphonyl, perfluoro, tertiary amino, and imido, and

(ii) an anhydride-terminated prepolymer of (I) and (II) having an weight average molecular weight of between about 1000 and 500,000, under condensation polymerization conditions to provide the copoly(amide acid oxetane).

4. A process for making a copoly(imide oxetane) comprising subjecting the copoly(amic acid oxetane) of claim 1 to imidization conditions.

5. The process of claim 4 wherein the imidization conditions comprise a thermal ring closure at a temperature of between about 150° C. and 400° C.

6. The process of claim 4 wherein the imidization conditions comprise a chemical ring closure in the presence of a ring-closing catalyst at a temperature between about −20° C. and 200° C.

7. The process of claim 6 wherein the ring-closing catalyst is pyridine, triethylamine, or acetic anhydride.

8. A copoly(imide oxetane) made by the process of claim 4 .

Assignees

• Nasa
• Us Adminstrator Of Nasa

Inventors

• Wohl Jr Christopher J
• Connell John W
• Siochi Emilie J
• Smith Jr Joseph G

Classifications

• C07D305/08 Primary

  with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring atoms · CPC title

• C09D179/08

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• C08G73/1042

  Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds · CPC title

• C08G73/105

  with oxygen only in the diamino moiety · CPC title

• C08G65/18

  Oxetanes · CPC title